JPS6038723A - Magnetic recording medium - Google Patents

Magnetic recording medium

Info

Publication number
JPS6038723A
JPS6038723A JP58144413A JP14441383A JPS6038723A JP S6038723 A JPS6038723 A JP S6038723A JP 58144413 A JP58144413 A JP 58144413A JP 14441383 A JP14441383 A JP 14441383A JP S6038723 A JPS6038723 A JP S6038723A
Authority
JP
Japan
Prior art keywords
radiation
parts
layer
magnetic
undercoat layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP58144413A
Other languages
Japanese (ja)
Inventor
Masaharu Nishimatsu
西松　正治
Toshiaki Ide
井出　敏秋
Yuichi Kubota
悠一 久保田
Yoshiaki Saito
斉藤　善明
Shigeru Shimada
茂 島田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Corp
Original Assignee
TDK Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TDK Corp filed Critical TDK Corp
Priority to JP58144413A priority Critical patent/JPS6038723A/en
Priority to US06/631,208 priority patent/US4596747A/en
Priority to DE3428943A priority patent/DE3428943C2/en
Publication of JPS6038723A publication Critical patent/JPS6038723A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
    • G11B5/733—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer characterised by the addition of non-magnetic particles
    • G11B5/7334—Base layer characterised by composition or structure
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
    • G11B5/733—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer characterised by the addition of non-magnetic particles
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
    • G11B5/739—Magnetic recording media substrates
    • G11B5/73923—Organic polymer substrates
    • G11B5/73927—Polyester substrates, e.g. polyethylene terephthalate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/90—Magnetic feature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Landscapes

  • Paints Or Removers (AREA)
  • Magnetic Record Carriers (AREA)

Abstract

PURPOSE:To improve the antistatic property and to make a surface layer or the like unnecessary by forming an undercoat layer contg. carbon black dispersed in radiation-curing oligomers or polymers each having one or more double bonds in one molecule on a transparent plastic support, curing the undercoat layer, and forming a magnetic layer on the cured undercoat layer. CONSTITUTION:An undercoat layer contg. 5-200pts.wt. carbon black dispersed in 100pts.wt. radiation-curing mixture is formed on the surface of a transparent plastic support of polyester or the like. The mixture consists of an acrylic, allyl or maleic acid oligomer or polymer having two or more double bonds which are cross-linked with radiation in one molecule and of an oligomer or polymer having one or more double bonds which undergoes radiation polymn. in one molecule. The undercoat layer is cured with radiation such as electron beams, and a magnetic layer is formed on the cured undercoat layer. A magnetic recording medium having superior durability is obtd. without requiring the formation of a surface layer on the magnetic layer or a back layer on the back side of the support.

Description

【発明の詳細な説明】 本発明は帯電防止性および表面平滑性に優れ、かつ良好
な電気的性質を有する磁気記録媒体の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a magnetic recording medium that has excellent antistatic properties and surface smoothness, and has good electrical properties.

現在オーディオ用テープ、ビデオ用テープ、磁気ディス
ク等の多くの磁気記録媒体は、ポリエステル、ポリ塩化
ビニル等のプラスチックフィルムまたは、紙等の基材フ
ィルム上に一酸化鉄等の磁化可能な金属粉を含む塗料を
塗布し、配向、乾燥カレンダーリング、必要に応じて硬
化の工程を経て作成されている。Currently, many magnetic recording media such as audio tapes, video tapes, and magnetic disks use magnetizable metal powder such as iron monoxide on plastic films such as polyester or polyvinyl chloride, or base films such as paper. It is created by applying a paint containing it, orientation, drying calendering, and if necessary curing.

この塗料用バインダーとして、種々の熱可塑樹脂または
熱硬化性樹脂が用いられているが、塗料中の顔料濃度が
高く、基材フィルム表面を良く濡らせないこと等の原因
で、接着性が弱くなり、例えば、テープに瞬間的に強い
応力が作用した時に磁性層が脱落することも起り得る。Various thermoplastic resins or thermosetting resins are used as binders for this paint, but the adhesiveness becomes weak due to the high pigment concentration in the paint and the inability to wet the base film surface well. For example, when a strong instantaneous stress is applied to the tape, the magnetic layer may fall off.

この接着力を高めることを目的に、基材フィルム上に非
磁性下塗り層（プライマ一層）を設けることが行なわれ
ている。プライマ一層形成の為に用いられる樹脂バイン
ダーに於いても、種々の熱可塑性樹脂ないしは熱硬化性
樹脂が用いられている。熱可塑性樹脂プライマーを泪い
た場合、多雪の溶剤を含有する磁性塗料の塗布時に、既
に形成されているプライマ一層が溶剤により彩潤ないし
溶解し、塗りムラを生じ、磁性層の平滑性が失なわれる
問題がある。熱硬化性樹脂プライマーを用いた場合、上
記の問題は避けられるが、長時間の加熱硬化処理を要す
る為に、連続して磁性層を形成することができないとい
う工業的な不利があった。In order to increase this adhesive strength, a nonmagnetic undercoat layer (one layer of primer) is provided on the base film. Various thermoplastic resins or thermosetting resins are used as the resin binder used for forming the primer layer. If a thermoplastic resin primer is wetted, when applying a magnetic paint containing a large amount of solvent, the already formed primer layer will be saturated or dissolved by the solvent, resulting in uneven coating and loss of smoothness of the magnetic layer. There is a problem that arises. When a thermosetting resin primer is used, the above-mentioned problems can be avoided, but there is an industrial disadvantage that a magnetic layer cannot be continuously formed because a long heat curing treatment is required.

磁気記録媒体のプライマー処理における上記の間［はプ
ライマー形成用バインダーとして、所定の放射線硬化性
樹脂を用いることにより、短時間処理により極めて良好
な、耐溶剤性、接着性を有するプライマ一層を形成し、
連続して磁性層を塗布し、表面平滑性、電気特性および
機械的強度に侵れた磁気記録媒体を得られる。During the above-mentioned primer treatment of magnetic recording media, by using a prescribed radiation-curable resin as a binder for forming the primer, a single layer of primer with extremely good solvent resistance and adhesiveness can be formed in a short time. ,
By continuously applying magnetic layers, a magnetic recording medium with improved surface smoothness, electrical properties, and mechanical strength can be obtained.

即ち、支持体に非磁性下塗り層（プライマ一層）を施し
た後・磁性層を形成してなる磁気記録媒体において、該
下塗り層が、例えば１分子中に（メタ）アクリ■イル基
を２個以上有し、（メタ）アクリロイル基１個当りの分
子量が２００以上であるオリゴマーもしくはポリマーの
１種もしくは２種以上、さらに必要に応じて溶剤もしく
は光重合開始剤を含有する塗料等の放射線硬化性塗料を
用い、放射線照射により形成されてなる磁気記録媒体に
より上記の効果が達成される。That is, in a magnetic recording medium formed by forming a magnetic layer after applying a non-magnetic undercoat layer (one layer of primer) to a support, the undercoat layer contains, for example, two (meth)acryyl groups in one molecule. Radiation curable paints, etc. containing one or more oligomers or polymers having a molecular weight of 200 or more per (meth)acryloyl group, and further containing a solvent or a photopolymerization initiator as necessary. The above effects can be achieved by a magnetic recording medium formed using paint and irradiation with radiation.

このようなプライマ一層用塗料は、基材に塗布した後に
放射線照射を行うことにより、瞬間的に、ラジカル重合
により、三次元網目借造を有する塗膜を形成し、磁性層
の塗布時に、溶剤による膨泗を起こすことなく、磁性層
の平滑性を保持できる。This kind of primer single-layer paint is applied to the base material and then irradiated with radiation to instantly form a paint film with a three-dimensional network structure through radical polymerization. The smoothness of the magnetic layer can be maintained without causing any swelling.

こうして得られる磁気記録媒体は表面平滑性がすぐれ、
接着性も良好であるが、テープとして走行させるときに
摩擦帯電を生じ、またテープ巻装体が走行するときに磁
性面がベース面から離れるときにいわゆる剥離帯電を生
じ、これによりゴミ、ホコリ、ベースや磁性面の微小な
削れ粉などが磁性面に付着してドロップアウトの原因と
なる。最近ではベースフィルムの厚さが１１μ程度以下
になるものもあって、その表面には極く薄い高性能磁性
層が形成されるから、磁気ヘッドとテープ磁性面とのス
ペーシングをできるだけ小さくして高周波まで記録する
必要が生じており、ゴミ、ホコリは微小でもスペーシン
グに大きく影響を与えてドロップアウトを生じるのであ
る。The magnetic recording medium obtained in this way has excellent surface smoothness,
Adhesion is also good, but frictional electrification occurs when the tape is run, and so-called peel-off electrification occurs when the magnetic surface separates from the base surface when the tape-wrapped body is run, which causes dirt, dust, etc. Minute shavings from the base or magnetic surface adhere to the magnetic surface and cause dropouts. Recently, some base films have a thickness of about 11 μm or less, and an extremely thin high-performance magnetic layer is formed on the surface of the base film, so the spacing between the magnetic head and the magnetic surface of the tape has to be made as small as possible. It is now necessary to record up to high frequencies, and even minute amounts of dirt and dust can greatly affect spacing and cause dropouts.

また・プライマ一層を介して薄い磁性層を設けた磁気記
録媒体は、光に対してかなりの透過性を示し、ビデオテ
ープ、計測テープ等においてオートストップ等の制御を
行う際の光学的な制御における誤動作の原因となる。In addition, magnetic recording media, which have a thin magnetic layer interposed between a single layer of primer, exhibit considerable transparency to light, resulting in malfunctions in optical control when performing auto-stop control on video tapes, measurement tapes, etc. It causes

これらの対策としては磁性面と反対のベース面にバック
層を形成し、該バックＮにカーボンブラック等の導電性
粉末を分散させておければ所定の導電性を有する磁気記
録媒体とすることができる。As a countermeasure against these problems, if a back layer is formed on the base surface opposite to the magnetic surface, and conductive powder such as carbon black is dispersed in the back layer, a magnetic recording medium having a predetermined conductivity can be obtained. can.

しかしながら、バック層はプライマ一層の他に別の層と
して形成されるものであるがら余分の工程を必要とする
。However, although the back layer is formed as a separate layer in addition to the primer layer, it requires an extra process.

本発明は上記のバック層を用いないで帯電性が低く・　
ドリップアウトの少ない磁気記録媒体を提供することを
目的とする。The present invention has low chargeability without using the above-mentioned back layer.
An object of the present invention is to provide a magnetic recording medium with less dripout.

簡単に述べると、本発明は放射線感応性（硬化性）の二
重結合を有る分子を含む放射線硬化性塗料にカーボンブ
ラックを分散させ、これをプライマ一層として用いるこ
とにより、帯電性の低い１表面平滑性の良い、接着性の
良い磁気記録媒体を提供できる。Briefly stated, the present invention involves dispersing carbon black in a radiation-curable paint containing molecules with radiation-sensitive (curable) double bonds, and using this as a primer layer to form a single surface with low chargeability. A magnetic recording medium with good smoothness and good adhesiveness can be provided.

磁性層の表面抵抗は、破性層に導電ｇｊ質が無くプライ
マー層のみに分散されている【こも拘らず大幅に減少し
て帯４とそれによるテープの粘りつきやドロップアウト
の問題、使用中及び製造工程中に巻姿の悪くなる問題を
解消することができるＯまた、カーボンブラックは記録
媒体を光不透過性にするから上述の誤検出しこよる誤動
作の問題を生じない。The surface resistance of the magnetic layer is because there is no conductive material in the rupture layer and it is dispersed only in the primer layer. Furthermore, since carbon black makes the recording medium opaque to light, the above-mentioned problem of erroneous detection and malfunction can be avoided.

本発明で用いる放射線硬化性塗料の信組成分としては、
１分子中に少くとも２個の放射線架橋性の二重結合を含
むもので、これらにはアクリル系二重結合、アリル系二
重結合、マレイン系二貫結合、その他の放射線架橋性の
二重結合を含むオリゴマーまたはポリマーが會まれる。The radiation curable paint used in the present invention has the following components:
Contains at least two radiation-crosslinkable double bonds in one molecule, including acrylic double bonds, allylic double bonds, maleic double bonds, and other radiation-crosslinkable double bonds. Oligomers or polymers containing linkages are assembled.

好適には分子内に２個以上の（メタ）アクリロイル基を
有し、（メタ）アクリロイル基１個当りの分子量が２０
０以上である化合物が使用されつる。（メタ）アクリロ
イル基１個当りの分子量が２００以下の場合には、架橋
硬化反応時に大きな体積収縮を生じ、基材がカールし、
寸法安定性が悪く、接着性が著じるしく低下することは
知られていることである。Preferably, the molecule has two or more (meth)acryloyl groups, and the molecular weight per (meth)acryloyl group is 20.
Compounds that are 0 or more are used. If the molecular weight per (meth)acryloyl group is 200 or less, large volumetric shrinkage occurs during the crosslinking and curing reaction, causing the substrate to curl.
It is known that dimensional stability is poor and adhesion is significantly reduced.

低分子量モノマーに於いては、神意の低い化合物も多く
、乾慄硬化時に蒸発飛散し、上京的に問題を起こす恐れ
がある。Among low-molecular-weight monomers, there are many compounds with low divine intent, and they may evaporate and scatter during dry-shock curing, causing problems in Tokyo.

しかし、このような低分子量子ツマ−でもより高分子垣
のものと併用することですぐれた特性を発揮できる。However, even such low-molecular-weight quantum materials can exhibit excellent properties when used in combination with polymer-based materials.

放射線硬化性オリゴマーまたはポリマーは２桟以上混合
して使用する場合には特に、 （ト）放射線により硬化性をもつＴ　Ｕ　Ｈ１ｔ二慮結
合を２個以上有する分子量５０００以上、好ましくは８
０００以上の化合物、 （１３）　放射線により硬化性をもつ不飽和二重結合を
１４ｖＡ以上有する分子ｉｊｉ　４００以上で、カッ５
０００未國、好ましくは６００〜３０００の化合物、（
Ｃ）　放射線により脱化性をも゛つ不飽和二重結合を１
個以上有する分子量４００未満の化合物、上記（ト）、
ＣＢ）、（Ｃ）から選ばれる少なくとも２ｍ以上を′ぷ
有する放射に泉硬化性塗料を用いるとすぐれた作用効果
が得られる。さらに、放射線硬化性塗料が（イ）、（Ｂ
）、（Ｃ）から３′Ｆｉばれる少なくとも２種以上を含
有し、かつ（Ａ）が０〜９０凧ｆ１％、（Ｂ）が０〜８
０ハ量％、（Ｃ）がθ〜５０嶌旦％の配合比率で用いる
と良い。また、放射線硬化性塗料が（ＮおよびＣＢ）を
含有し、（４）が２０〜９５竜鍬％、（Ｂ）が５〜８０
重量％の配合比率も可能である。さらに、成射線硬化住
塗眉は１〜１０八量％の光重合増感剤を含有しても良い
。Particularly when the radiation-curable oligomer or polymer is used in combination of two or more frames,
000 or more, (13) A molecule with an unsaturated double bond that is curable by radiation and has an iji of 400 or more and has a radiation curable unsaturated double bond of 14 vA or more.
000 countries, preferably 600 to 3000 compounds, (
C) 1 unsaturated double bond that is deoxidizable by radiation
A compound having a molecular weight of less than 400, the above (g),
Excellent effects can be obtained by using a spring-curing paint selected from CB) and (C) that has a radiation radius of at least 2 m or more. Furthermore, radiation-curable paints (A) and (B)
), contains at least two or more types of 3'Fi from (C), and (A) is 0 to 90 kite f1%, and (B) is 0 to 8
It is preferable to use the compound at a blending ratio of 0% by amount and (C) from θ to 50%. In addition, the radiation-curable paint contains (N and CB), (4) is 20-95%, and (B) is 5-80%.
A blending ratio of % by weight is also possible. Furthermore, the radiation-cured Sumitomo eyebrows may contain 1 to 10% by weight of a photopolymerizable sensitizer.

これらの化合物の例は次の通りである。Examples of these compounds are:

分子中に水酸基を１個以上有する化合物１分子に１分子
以上のポリイソシアネート化合物のひとつのイソシアネ
ート基を反応させ、次にインシアネート基と反応する基
及び放射線硬化性を有する不飽和二重結合を有する単景
体１分子以上との反応物、例えばプロピレングリコール
にプルピレンオキサイドを付加した二官能性のポリエー
テル（アデカポリエーテルＰ１００Ｄ旭電化社製）１モ
ルにトルエンジイソシアネート２モルを反応させ、その
後２モルの２−ヒトルキシエチルメタクリレートを反応
させて得た分子末端にアクリル系二重結合を２個有する
樹ｌｉｔ’／　１プレポリマー、オリゴマーもしくはテ
ロマーを小げることができる。One molecule of a compound having one or more hydroxyl groups in the molecule is reacted with one isocyanate group of one or more molecules of a polyisocyanate compound, and then a group that reacts with the incyanate group and an unsaturated double bond that has radiation curability are added. 2 moles of toluene diisocyanate are reacted with 1 mole of a bifunctional polyether (ADEKA Polyether P100D manufactured by Asahi Denka Co., Ltd.) obtained by adding propylene oxide to propylene glycol, and then It is possible to reduce the size of a lit'/1 prepolymer, oligomer or telomer having two acrylic double bonds at the molecular end obtained by reacting 2 moles of 2-hydroxyethyl methacrylate.

ここで使用される水酸基を１個以上含有する化合物とし
ては、アデカポリエーテルＰ−７００、アデカボリエー
テルＰ−１０００、アデヵポリエーテルＧ−１５００（
以上旭電化社製）、ポリメグ１０００、ポリメグ６５０
（以上クオーカ〜・フーツ社製）等の多官能性ポリエー
テル類書ニトロセルローズ、アセチルセルルーズ、エチ
ル七ルローズの様な紬維累誘導体蓄ビニライトＶＡＧＨ
（米国ユニオンカーバイド社ｌ！！Ｊ）の様な水酸基を
有する一部ケン化された塩化ビニル−酢酸ビニル共重合
体寥ポリビニルアルコール蓚ポリビニルホルマール寥ポ
リビニルブチラール寥ポリカブｐラクトンＰＣＰ−ｏ２
ｏｏ、ポリカプロラクトンＰＣＰ−０２４０、ポリカプ
ロラクトンｐｃｐ−ｏ３ｏ口（以上チッソ社＠）等の多
官能性ポリエステル類蓼フタル酊、イソフタル酸、テレ
フタル酸、アジピン酸、コハク酸、セパチン酸のような
飽和多塩基酸とエチレングリコール、ジエチレングリコ
ール、１．４−ブタンジオール、１．３−ブタンジオー
ル、１，２−プロピレングリコール、ジプロピレングリ
コール、１６−ヘキサンクリコール、ネオペンチルグリ
コール１グリセリン、トリメチロールプロパン、ペンタ
エリスリットのような多価アルコールとのエステル結合
により得られる飽和ポリエステル樹脂８水酸基を含有す
るアクリルエステルおよびメタクリルエステルを少なく
とも一株以上重合成分として含むアクリル糸重合体を拳
げることができる。Compounds containing one or more hydroxyl groups used here include ADEKA Polyether P-700, ADEKA Polyether P-1000, ADEKA Polyether G-1500 (
(manufactured by Asahi Denka Co., Ltd.), Polymeg 1000, Polymeg 650
Polyfunctional polyethers such as (manufactured by Quoka-Foots Co., Ltd.), pongee fiber derivatives such as nitrocellulose, acetyl cellulose, and ethyl hexarurose vinylite VAGH
Partially saponified vinyl chloride-vinyl acetate copolymer with hydroxyl groups such as (U.S. Union Carbide Corporation l!!J) Polyvinyl alcohol Polyvinyl formal Polyvinyl butyral Polycab plactone PCP-o2
polyfunctional polyesters such as polycaprolactone PCP-0240, polycaprolactone pcp-o3o (all of which are from Chisso Corporation); saturated polyesters such as isophthalic acid, terephthalic acid, adipic acid, succinic acid, and cepatic acid; Basic acid and ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-propylene glycol, dipropylene glycol, 16-hexane glycol, neopentyl glycol 1 glycerin, trimethylolpropane, penta A saturated polyester resin obtained by ester bonding with a polyhydric alcohol such as erythritol An acrylic yarn polymer containing at least one acrylic ester and methacrylic ester containing 8-hydroxyl groups as a polymerization component can be produced.

また、ここで使用されるポリイソシアネート化合物とし
ては、２．４−トルエンジイソシアネート、２．６−ト
ルニンジイソシアネー）、１．４−キシレンジイソシア
ネート、ｍ−フ二二レンジイソシアネート、ｐ−フェニ
レンジイソシアネート１ヘキサメチレンジイソシアネー
ト、インホロンジイソシアネートやデスモジュールＬデ
スモジュールｉＬｔ西ドイツバイエル社製）等がある。In addition, the polyisocyanate compounds used here include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,4-xylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, Examples include hexamethylene diisocyanate, inphorone diisocyanate, and Desmodur L (manufactured by Bayer AG, West Germany).

インシアネート基と反応する基および放射線値化性不飽
和二重結合を有する単Ｈｋ体としては、アクリル酸ある
いはメタクリル酸の２−ヒドロキシエチルエステル、２
−ヒドロキシプロピルエステル、２−ヒドロキシオクチ
ルエステル等水酸基を有するエステル類１アクリルアマ
イド、メタクリルアマイド、Ｎ−メチロールアクリルア
マイド等のイソシアネー）基と反応する活性水素を持ち
かつアクリルアルコール、マレインＱ多価アルコールエ
ステル化合物、不飽和二重結合を有する長鎖脂肪酸のモ
ノあるいはジグリセリド等イソシアネー）基と反応する
活性水嵩を持ちかつ放射線硬化性を有する不飽和二重結
合を含有する単１１１体も含まれる。Examples of the single Hk compound having a group that reacts with an incyanate group and a radiation-valueable unsaturated double bond include 2-hydroxyethyl ester of acrylic acid or methacrylic acid, 2-hydroxyethyl ester of acrylic acid or methacrylic acid,
- Esters with hydroxyl groups such as hydroxypropyl ester and 2-hydroxyoctyl ester (1) Acrylic alcohol, maleic polyhydric alcohol ester with active hydrogen that reacts with isocyanate groups such as acrylamide, methacrylamide, N-methylol acrylamide, etc. It also includes compounds containing unsaturated double bonds that have an active water volume that reacts with mono- or diglyceride (isocyane) groups of long-chain fatty acids that have unsaturated double bonds, and that are radiation-curable.

分子中にエポキシ基を１個以上含む化合物１分子と、エ
ポキシ基と反応する基および電子線硬化性不飽和二重結
合を有する単量体１分子以上との反応物、例えばグリシ
ジルメタクリルレートをラジカル重合させて得たエポキ
シ基を含有する熱可塑性樹脂ｊ）１にアクリル酸を反応
させ、カルボキシル基とエポキシ基との開環反応により
、分子中にアクリル系二重結合をベンタントさせた樹脂
、プレポリマーもしくはオリゴマー、また、マレイン酸
を反応させカルボキシル基とエポキシ基との開環反応に
より分子骨格中に放射線硬化性不飽和二重結合を有する
樹脂、プレポリマー、オリゴマーを挙げることができる
。A reaction product of one molecule of a compound containing one or more epoxy groups in the molecule and one or more molecules of a monomer having a group that reacts with the epoxy group and an electron beam curable unsaturated double bond, such as glycidyl methacrylate, is used as a radical. A thermoplastic resin containing an epoxy group obtained by polymerizationj) 1 is reacted with acrylic acid, and an acrylic double bond is bent in the molecule by a ring-opening reaction between a carboxyl group and an epoxy group. Polymers or oligomers, as well as resins, prepolymers, and oligomers having radiation-curable unsaturated double bonds in their molecular skeletons by reaction with maleic acid and ring-opening reaction between carboxyl groups and epoxy groups can be mentioned.

ここで分子中にエポキシ基を１個以上含む化合物として
は、グリシジルアクリレート、グリシジルメタクリレー
トの如きエポキシ基を含むアクリルエステルあるいはメ
タクリルエステルノホ％　ｔ：リマーあるいは他の重合
性モノマーとの共重合体ｉエビツー）８２Ｂ、エピコー
ト１００１、エビツー）１００７、エピコート１００９
（以上シェル化学社製）等その他種々のタイプのエポキ
シ樹脂等がある。Here, examples of compounds containing one or more epoxy groups in the molecule include acrylic esters or methacrylic esters containing epoxy groups such as glycidyl acrylate and glycidyl methacrylate. ) 82B, Epicort 1001, Ebitwo) 1007, Epicort 1009
(manufactured by Shell Chemical Co., Ltd.) and various other types of epoxy resins.

エポキシ基と反応する基および放射ね砂化性不飽和二重
結合を有する単ｆ、に体としてはアクリル■、メタクリ
ル酸等のカルボキシル基を含有するアクリル糸車Ｈ体、
メチルアミ／エチルアクリレート、メチルアミノメタク
リレート等の第１級もしくは第２級アミ７基を有するア
クリル単量体に加えマレイン酸、フマル酸やクロトンｈ
々、ウンデシレン酸等放射線硬化性不飽和二重帖合を有
する多塩基酸単量体も使用できる。Examples of single F-form bodies having a group that reacts with an epoxy group and an unsaturated double bond capable of turning into sand by radiation, acrylic ■ bodies, acrylic spinning wheel H bodies containing carboxyl groups such as methacrylic acid,
In addition to acrylic monomers having 7 primary or secondary amide groups such as methylamino/ethyl acrylate and methylaminomethacrylate, maleic acid, fumaric acid and croton h
Polybasic acid monomers having radiation-curable unsaturated double bonds such as undecylenic acid can also be used.

ＩＩ分子中にカルボキシル基を１個以上含む化合物１分
子とカルボキシル基と反応する基および放射線硬化性不
飽和二重結合を有する単量体１分子以上との反応物、例
えばメタクリル酸を溶液重合させて得たカルボキシル基
を含有する熱可塑性樹脂にグリシジルメタクリレートを
反応させ、第ＩＩ項と同様にカルボキシル基とエポキシ
基の開環反応により分子中にアクリル系二重結合を導入
させた樹脂、プレポリマー、オリゴマーを挙げることが
できる。II Solution polymerization of one molecule of a compound containing one or more carboxyl groups in the molecule and one or more molecules of a monomer having a group that reacts with carboxyl groups and one or more monomers having a radiation-curable unsaturated double bond, such as methacrylic acid. A resin or prepolymer obtained by reacting glycidyl methacrylate with a thermoplastic resin containing a carboxyl group obtained by the method of , oligomers.

分子中にカルボキシル基を１個以上含む化合物としては
、分子鎖中または分子末端にカルボキシル基を斥むポリ
エステル類ｔアクリル酸、メタクリル酸、無水マレイン
酸、フマル酸等のラジカル重合性を持ち、かつカルボキ
シル基を有する単量体のホモポリマーあるいは他の重合
性モノマーとの共重合体等である。Compounds containing one or more carboxyl groups in the molecule include polyesters that have carboxyl groups in the molecular chain or at the end of the molecule, have radical polymerizability such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid, and These include homopolymers of monomers having carboxyl groups or copolymers with other polymerizable monomers.

カルボキシル基と反応する基および放射線硬化性不飽和
二点結合を有する単量体としてはグリシジルアクリレー
ト、グリシジルメタクリレ−を等がある。Examples of the monomer having a group that reacts with a carboxyl group and a radiation-curable unsaturated two-point bond include glycidyl acrylate and glycidyl methacrylate.

■　分子鎖中に放射線硬化性不飽和二重結合を含有する
ポリエステル化合物、例えば第１項に記載の多塩基１２
と多価アルコールのエステル結合から成る飽和ポリエス
テル樹脂で多塩基酸の一部をマレイン酸とした放射線硬
化性不飽和二重結合を含有する不飽和ポリエステル樹脂
、プレポリマー、オリゴマーを拳けることができる。■ A polyester compound containing a radiation-curable unsaturated double bond in its molecular chain, such as the polybase 12 described in item 1.
A saturated polyester resin consisting of an ester bond of a polyhydric alcohol and a polybasic acid, and a part of the polybasic acid is maleic acid, and can be used to form unsaturated polyester resins, prepolymers, and oligomers containing radiation-curable unsaturated double bonds. .

飽和ポリエステル樹脂の多塩基ｒβおよび多価アルコー
ル成分は第１項に記載した各化合物を挙げることができ
、放射線硬化性不飽和二重結合としてはマレイン酸、フ
マル醒等を誉げることができる。Examples of the polybasic rβ and polyhydric alcohol components of the saturated polyester resin include the compounds listed in Section 1, and examples of radiation-curable unsaturated double bonds include maleic acid and fumaric acid. .

放射腺硬化性不飽和ポリエステル樹ｔｌｉ？の製法は多
塩基ａ成分１１（【以上と多価アルコール成分１種以上
にマレイン除゛、７マル斂等を加え常法、すなわち触媒
存在下１８０〜２００℃窒素雰囲気下脱水あるいは脱ア
ルコール反応のｐ、２４０〜２８０℃まで昇温し、０．
５〜ｉ　ｍｍＨＨの減圧下縮合反応によりポリエステル
樹脂を得ることができる。マレイン酸やフマル酸等の含
有ガ２は、製造時の架橋、放射線硬化性等から酸成分中
１〜４０モル％で好ましくは１０〜５０モル％である。Radiation hardening unsaturated polyester tree tli? The method for producing polybasic component a is to add maleic acid, 7-marine, etc. to the above and one or more polyhydric alcohol components, and perform a dehydration or dealcoholization reaction in the presence of a catalyst at 180 to 200°C in a nitrogen atmosphere. p, the temperature was raised to 240-280°C, and 0.
A polyester resin can be obtained by condensation reaction of 5 to i mmHH under reduced pressure. The content of the acid 2, such as maleic acid or fumaric acid, is 1 to 40 mol%, preferably 10 to 50 mol%, in the acid component due to crosslinking and radiation curability during production.

■　放射線硬化性不飽和二重結合を有する低分子量の化
合物も目的に応じ使用が可能であり、そのような低分子
量の化合物としては、スチレン、エチルアクリレート、
エチレングリコールジアクリレート、エチレングリコー
ルジメタクリレート、ジエチレングリコールジアクリレ
ート、ジエチレングリコールジアクリレート −ヘキサングリコールジアクリレート、１．６−ヘキサ
ンゲリコールジメタクリレート、トリメチロールプロパ
ントリアクリレート、トリメチロールプロパントリメタ
クリレート等が挙げられる（なお、第ｖ項の化合物は主
として（Ｃ）の化合物である）。■ Low molecular weight compounds with radiation-curable unsaturated double bonds can also be used depending on the purpose; such low molecular weight compounds include styrene, ethyl acrylate,
Examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol diacrylate-hexane glycol diacrylate, 1,6-hexane gelicold dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, etc. , the compound of item v is mainly a compound of (C)).

本発明に於ける放射線硬化性塗料としては第１項から第
７項に記載した化合物を使用して得られるが、アクリル
系二重結合を含む分子ｆｉ４００以上の化合物を単独に
用いてもよいがその場合には、分子量が大きくなるにつ
れ官能基密度から電子線硬化性が低下する傾向となり゛
、従って高綜泣が必要となり、硬化性が低下すると耐熱
性も劣る傾向にある。また、接着性については硬化性が
高（なると低下する場合がある。The radiation-curable paint in the present invention can be obtained by using the compounds described in Items 1 to 7, but a compound containing an acrylic double bond and having a molecular fi of 400 or more may be used alone. In this case, as the molecular weight increases, the electron beam curability tends to decrease due to the functional group density, thus requiring high weeping, and as the curability decreases, the heat resistance also tends to deteriorate. In addition, with regard to adhesion, if the curability is high (it may decrease).

一方、４００未満の分子量の電子線硬化性樹脂の場合に
は、電子線硬化性が良好で耐溶剤性耐熱性等が良好とな
るが、接着性に問題がある。このようにアクリル系二重
結合を含む分子量４００以上あるいは４００未満の化合
物を単独で使用する場合、磁気記録媒体に要求される多
岐に渡る特性をバランス良く満足し得るアンダーコート
用塗料を得ることが難しい。On the other hand, in the case of an electron beam curable resin having a molecular weight of less than 400, the electron beam curability is good and the solvent resistance, heat resistance, etc. are good, but there is a problem in adhesiveness. In this way, when a compound containing an acrylic double bond and having a molecular weight of 400 or more or less than 400 is used alone, it is difficult to obtain an undercoat paint that satisfies the wide variety of properties required for magnetic recording media in a well-balanced manner. difficult.

これに対し、分子量の異なる化合物の２　ａｉ以上を配
合すると、良好なりｆ！着性および硬化性が得られるも
のである。On the other hand, when 2 ai or more of compounds with different molecular weights are blended, the results are good. It provides adhesion and curability.

本発明では必要に応じ、非反応性溶剤が使用される溶剤
としては特に制限はないが、バインダーの溶解性および
相溶性等を考慮して適宜選択される。例えばアセトン、
メチルエチルケトン、メチルイソブチルケトン、シクロ
ヘキサノン等のケトン類、ギ酸エチル、酢酸エチル、酢
酸ブチル等のエステル類、メタノール、エタノール、イ
ソプロパツール、ブタノール等のアルコール類、トルエ
ン、キシレン、エチルベンゼン等の芳香族炭化水素類、
イソプルピルエーテル、エチルエーテル、ジオキサン等
のエーテル類、テＦラヒドロ７ラン、フルフラール等の
７ラン類等を単一溶剤またはこれらの混合溶剤として用
いられる。In the present invention, if necessary, a non-reactive solvent is used. Although there is no particular restriction on the solvent, it is appropriately selected in consideration of the solubility and compatibility of the binder. For example, acetone
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, and butyl acetate; alcohols such as methanol, ethanol, isopropanol, and butanol; and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. kind,
Ethers such as isopropylether, ethyl ether, and dioxane, and heptadanes such as teFlahydro heptane and furfural are used as a single solvent or a mixed solvent thereof.

本発明に係わる磁性層としては、熱硬化性樹脂、熱硬化
性樹脂をベヒクルとするものは勿論、プライマ一層に用
いられているような放射線硬化性樹脂を使用し、放射線
照射により影成するものであってもよく、プライマーお
よび磁性層への放射線照射を一度に行なうこともできる
。The magnetic layer according to the present invention may not only be a thermosetting resin or one using a thermosetting resin as a vehicle, but also one that uses a radiation-curable resin such as that used in the primer layer and is shaded by radiation irradiation. It is also possible to irradiate the primer and the magnetic layer with radiation at the same time.

本発明に係わるプライマ一層および磁性塗料が塗布され
る基体としては、現在磁気記録媒体用基材として広く活
用されているポリエチレンテレフタレート系フィルム、
更に耐熱性を要求される用途としてはポリイミドフィル
ム、ポリアミドフィルム等が活用される。特にポリエス
テｌＬＩ系フィルムにおいては薄物ベースでは・１軸延
伸、２軸延伸処理をほどこして利用するケースも多い。The substrate on which the single layer of primer and the magnetic paint according to the present invention are applied include polyethylene terephthalate film, which is currently widely used as a substrate for magnetic recording media;
Further, for applications requiring heat resistance, polyimide films, polyamide films, etc. are used. Particularly in the case of polyester ILI-based films, thin films are often subjected to uniaxial stretching or biaxial stretching.

また紙にコーティングをほどこす用途も有る。It is also used to coat paper.

本発明に係わる放射線硬化塗料の架机、硬化に使用する
放射線としては、電子線加速器を線源とした電子線Ｇｏ
を線源としたｒ−線、ｓｒを線源としたρ−線、Ｘ線発
生器を線源とし７．ｍ　Ｘ拶および紫外線が使用される
。特に照射線源としては吸収線量の制御、製造工程ライ
ンへの尋人、電離放射線の遮閉等の見地から、電子線加
速器による電子線あるいは紫外線を使用する方法が有利
である。The radiation used for the radiation curable paint frame and curing according to the present invention is an electron beam Go using an electron beam accelerator as a radiation source.
7. R-rays using sr as a radiation source, ρ-rays using sr as a radiation source, and X-ray generator as a radiation source. mx radiation and ultraviolet light are used. In particular, as an irradiation source, it is advantageous to use electron beams from an electron beam accelerator or ultraviolet rays from the viewpoints of controlling the absorbed dose, allowing personnel to access the manufacturing process line, and blocking ionizing radiation.

磁性塗膜を硬化する際に使用する奄子勝特性としては、
透過力の自から加速電圧１００〜７５０ＫＶ　、好まし
くは１５０〜５００　ＫＶ　ｃ／）　’Ｑ１．−Ｔ−８
加連器を用い、吸収線量を０，５〜２０メガラッドにな
る様に照射するのが好都合である。The Amakatsu properties used when curing magnetic coatings are as follows:
Due to the penetrating power, the acceleration voltage is 100 to 750 KV, preferably 150 to 500 KV c/) 'Q1. -T-8
It is convenient to apply the radiation using a radiator so that the absorbed dose is between 0.5 and 20 megarads.

本発明の放射ＣＡ硬化性塗料は光重合１９１感剤を加え
ることにより紫外線硬化を行なうこともできる。The radiation CA curable paint of the present invention can also be cured by ultraviolet rays by adding a photopolymerizable 191 sensitizer.

該光重合増感剤としては従来公知のものでよく、０え４
ｆ　ベンゾインエチルエーテル、ベンゾインエチルエー
テル、α−メチルベンゾインα−クロルデオキシベンゾ
イン等のベンゾイン系、ベンゾフェノン、アセ）フェノ
ンビスジアルキルアミノベンゾフェノン等のケトン類、
アン）ラキノン、フエナントラキ／ン等のキノン類、ベ
ンジルジスルフィド、テトラメチルチウラムモノスルフ
ィド等のスルフィド類、得を挙げることができる。光重
合増感剤は、樹脂固形分に対し、ａ１〜１０％の範囲が
望ましい。The photopolymerization sensitizer may be a conventionally known one, and
f benzoin series such as benzoin ethyl ether, benzoin ethyl ether, α-methylbenzoin α-chlordeoxybenzoin, ketones such as benzophenone, ace)phenone bisdialkylaminobenzophenone,
Examples include quinones such as anthraquinone and phenanthraquinone, and sulfides such as benzyl disulfide and tetramethylthiuram monosulfide. The photopolymerization sensitizer is desirably in the range of a1 to 10% based on the solid content of the resin.

以下、実施例および比較例により本発明を具体的に説明
する。なお、０中「部」、１％」とあるのは亜ｆｔ部、
重ＪＲ％を示す。Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. In addition, ``part'' in 0, 1%'' refers to the sub-ft part,
Shows heavy JR%.

実工・１ｉ１１例に先立ち、樹脂合成例を示す０樹脂合
成例（ａ） 塩化ビニル／酢酸ビニル／ビニルアルコールが９３／２
１５重景％の組成で分子量１８０００の共重合体１００
部をトルエン２３８部シクロヘキサノン９５部を加熱溶
解後、８０°Ｃに昇湿し、下記ＴＤＩアダクトを７．５
部加え、ざらにオクチル酸スズα００２部、ハイドルキ
ノン０．００２部加え、８２℃でＮ、ガス気流中インシ
アネー）（ＮＧＯ）反応率が９０％以上となるまで反応
せしめる。反応終了後冷却しメチルエチルケトン２３８
部を加え柿釈する。得られた樹脂組成物を（ａ）とする
。なお、この樹脂の分子ｉ辻は１９２００であり、メタ
アクリロイル基１個当りの分子量は約４４００である０ ＴＤＩアダクトの合成 トリレンジイソシアネー）　（ＴＤＩ）５４８部をＮｔ
ｎ流中１ノの４つロフラスコ内８０℃に加熱後、２−と
ド日キシエチルメタクリレート（２Ｉ（ＥＭＡ　）２６
０部、オクチル酸スズ０．０７部、ハイドロキノンＱ、
０５部を反応缶内の温度が８０〜８５′Ｇとなる様に冷
却コントロールしながら滴下し、滴下終了俄８０℃で３
時間攪拌し反応を完結させる。反応終了後取り出し、冷
却後、白色ペースト状のＴＤＩの２１（ＥＭＡアダク）
を得た。0 Resin synthesis example showing a resin synthesis example (a) Vinyl chloride/vinyl acetate/vinyl alcohol 93/2 prior to the practical 1i11 example
Copolymer 100 with a molecular weight of 18,000 and a composition of 15%
After heating and dissolving 238 parts of toluene and 95 parts of cyclohexanone, the temperature was raised to 80°C, and 7.5 parts of the following TDI adduct was dissolved.
002 parts of tin octylate α and 0.002 parts of hydroquinone were added to the colander, and the mixture was allowed to react at 82° C. until the reaction rate (NGO) in a N gas stream reached 90% or more. After the reaction is completed, cool and methyl ethyl ketone 238
Add part and mix. The obtained resin composition is referred to as (a). The molecular weight of this resin is 19,200, and the molecular weight per methacryloyl group is approximately 4,400.
After heating to 80°C in a four-volume flask in a stream of
0 parts, tin octylate 0.07 parts, hydroquinone Q,
05 parts was added dropwise while controlling the cooling so that the temperature inside the reaction vessel was 80 to 85'G, and the temperature was kept at 80°C for 30 minutes until the addition was completed.
Stir for an hour to complete the reaction. After the reaction is completed, take out and cool, white paste TDI 21 (EMA Adak)
I got it.

樹脂合成例（ｂ） 飽和ポリエステル樹脂（ダイナミートノーベル社製Ｌ−
４１１）１００部をトルエン１１６部、メチルエチルケ
トン１１６部に加熱溶解し、８０℃昇温後、樹脂合成例
（ａ）に帛じて合成したインホロンジイソシアネートー
アダク）２．８４部を加えオクチル酸スズ０．００６部
、ハイドルキノン０、００６部をさらに加え、Ｎ、ガス
気流中８０℃でＮＧＯ反応率９０％以上となるまで反応
せしめる。Resin synthesis example (b) Saturated polyester resin (L- manufactured by Dynamite Nobel)
411) 100 parts were dissolved in 116 parts of toluene and 116 parts of methyl ethyl ketone, and after raising the temperature to 80°C, 2.84 parts of inphorone diisocyanate adduct) synthesized according to Resin Synthesis Example (a) was added, and octylic acid was added. 0.006 parts of tin and 0.006 parts of hydroquinone are further added, and the mixture is allowed to react at 80° C. in a N gas stream until the NGO reaction rate reaches 90% or more.

得られた樹脂組成物を（Ｃ）とする。この樹脂の分子量
は２０６００である。The obtained resin composition is designated as (C). The molecular weight of this resin is 20,600.

樹脂合成例（６） テレフタル酸ジメチル２９ｔ２部、イソフタル酸ジメチ
ル２９１２部、マレイン酸ジメチル６４．８部、エチレ
ングリコール２５ｔ２部、１．４−ブタンジオール５６
４．８部、ｔ３−ブタンジオール８ｉ２部およびテトラ
−ｎ−ブチルチタネート４．０部を反応缶に仕込みＮ、
ガス気流中１８０℃で脱メタノール反応の後、２４０〜
２６０℃まで昇温し０．５〜１　ｍｍＨｇの減圧下縮合
反応により分子量８００００線状不飽和ポリエステル樹
脂を得た。Resin synthesis example (6) Dimethyl terephthalate 29t2 parts, dimethyl isophthalate 2912 parts, dimethyl maleate 64.8 parts, ethylene glycol 25t2 parts, 1,4-butanediol 56 parts
4.8 parts of t3-butanediol, 2 parts of t3-butanediol, and 4.0 parts of tetra-n-butyl titanate were charged into a reaction vessel.
After demethanol reaction at 180°C in a gas stream, 240~
A linear unsaturated polyester resin having a molecular weight of 80,000 was obtained by a condensation reaction at a temperature of 260° C. and a reduced pressure of 0.5 to 1 mmHg.

樹脂合成例（ｄ） ＮＩＡＸポリオールＰＣＰ−０２００（チッソ社製ポリ
カプロラクトン）２５０部、２−ヒドロキシエチルメタ
クリレート１２２．２部、ハイドルキノンα０２４部、
オクチル酸スズ０．　Ｏ３５部を反応缶に入れ、８０℃
に加熱？６解後、ＴＤ１１６五６部を反応缶内の温度が
８０〜９０゛Ｃとなる様に冷却しながら滴下し、滴下終
了後８０’ＣでＮＧＯ反応率９５％以上となるまで反応
せしめる。得られた樹脂組成物を（ｄ）とする。Resin synthesis example (d) 250 parts of NIAX polyol PCP-0200 (polycaprolactone manufactured by Chisso Corporation), 122.2 parts of 2-hydroxyethyl methacrylate, 24 parts of hydroquinone α0,
Tin octylate 0. Put 35 parts of O into a reaction vessel and heat to 80°C.
Heated to? After the completion of the reaction, 56 parts of TD116 were added dropwise while cooling the reaction vessel to a temperature of 80 to 90°C, and after the dropwise addition was completed, the reaction was allowed to occur at 80°C until the NGO conversion rate reached 95% or more. The obtained resin composition is referred to as (d).

この樹脂の分子ＭＬは１１４ｏである。この樹脂のメタ
アタリソイル２！！１個当りの分子量は約６００である
。The molecule ML of this resin is 114o. This resin Meta Atari Soil 2! ! The molecular weight per piece is about 600.

樹脂合成例（ｅ） 無水フタル酸１４８部、ｔ３−ブタンジオール６５ｓ１
エチレングリコール５θ部およびパラトルエンスルホン
酸２．５部を反応缶に仕込みＮ、７ガス気流下に１５０
℃で１時間次いで１８０℃で５時１ｔｕエステル化反応
の後、１００℃に冷却しハイドロキノンα３部アクリル
酸２８部を加え１５時間エステル化反応を行い、分子８
’４２０００のオリゴエステルアクリレートを得た。こ
の樹脂σ〕アクリロイル基１個当りの分子量は約６５０
である。Resin synthesis example (e) 148 parts of phthalic anhydride, 65s1 of t3-butanediol
5θ parts of ethylene glycol and 2.5 parts of para-toluenesulfonic acid were placed in a reaction vessel and heated to 150% under a stream of N, 7 gas.
After esterification reaction at 180°C for 1 hour and 1tu for 5 hours, it was cooled to 100°C, 3 parts of hydroquinone α and 28 parts of acrylic acid were added, and the esterification reaction was carried out for 15 hours.
'42,000 oligoester acrylate was obtained. The molecular weight of this resin σ] per acryloyl group is approximately 650
It is.

樹脂合成例（ｆ） アデカポリエーテルＰ−１０００（旭電化社Ｉポリエー
テル）２５０部、２−ヒト田キシエチルメタクリレ−）
６５部、ノ１イドロキノン０．０１３ｍ、オクチル酸ス
ズ０．０１７部を反応缶に入れ、８０℃に加熱浴ｈ′を
後、Ｔ　Ｄ　Ｉ　８７．０部を反応缶内の温度力（８０
〜９０′Ｃとなるように冷却しながらｆ２ｉ下し、諾下
終了後８０℃でＮＧＯ反応串９５％以上となるまで反応
せしめる。得られた樹脂組成物を（ｆ）とする。この樹
脂の分子量は１６１０、メタアクリロイル基１個当りの
分子ｆ工は約８００である。Resin synthesis example (f) 250 parts of Adeka Polyether P-1000 (Asahi Denka I Polyether), 2-Hydenoxyethyl methacrylate)
65 parts of 1-hydroquinone, 0.013 m of tin octylate, and 0.017 parts of tin octylate were placed in a reaction vessel, and heated to 80°C in a heating bath h'.
The mixture was heated to f2i while cooling to ~90'C, and after the reaction was completed, the mixture was allowed to react at 80°C until the NGO reaction rate reached 95% or more. The obtained resin composition is designated as (f). The molecular weight of this resin is 1,610, and the molecular weight per methacryloyl group is about 800.

上記の尉脂及び場合によりこれと上記■の成分に分散さ
せるカーボンブラックは平均粒子径１０〜３００μのも
のを、樹脂分１００部当り、約５〜２００部の割合で用
いる。光透過の面からは・カーボンブラックは約１０部
以上含有されていれば良く、帯電防止の面からは約５部
以上含有されていれば良い。例えば磁性層に合金磁、性
針状粉末を分散させ、乾燥厚３μに塗布した磁性層と、
乾燥厚ｌ１１１μに塗布したプライマ一層との組合せで
は、樹脂１００重量部当り約１０重量部のカーボンブラ
ックで光透過率を１％以下に抑えることができる。しか
もこのとき磁性層の表面抵抗はカーボンブラックがない
プライマ一層を用いた場合の１０１１ρ／Ｃｌ１１！が
１０′１〜１０１２／傭２に低下することが分った。The carbon black to be dispersed in the above-mentioned fat and optionally it and the above-mentioned component (2) has an average particle size of 10 to 300 microns, and is used in a proportion of about 5 to 200 parts per 100 parts of the resin. From the viewpoint of light transmission, it is sufficient that carbon black is contained in an amount of about 10 parts or more, and from the viewpoint of antistatic properties, it is sufficient that it is contained in an amount of about 5 parts or more. For example, a magnetic layer in which alloy magnetism and acicular powder are dispersed and coated to a dry thickness of 3μ,
In combination with a single layer of primer coated to a dry thickness of l111μ, the light transmittance can be suppressed to 1% or less with about 10 parts by weight of carbon black per 100 parts by weight of resin. Moreover, at this time, the surface resistance of the magnetic layer is 1011ρ/Cl11 when using a single layer of primer without carbon black! It was found that the value decreased from 10'1 to 1012/2.

実施例１ 前記樹脂組成物（ａ）４０部とカーボンブラック（２部
ｍｐ）４１ｆｌＳと溶剤（）ルエン／メチルエチルケト
ン＝１／１）Ｓ０部とを混合溶解させ、放射線硬化性塗
料を調製した。この塗料をポリエステルフィルム上に乾
燥膜厚α５μになるように塗布し、乾燥を行った後にＥ
ＳＩ社製エレクトロカーテン型電子線照射装置を用いて
、照射線量２Ｍｒａｄの条件でＮ、雰囲気下で電子腺照
射を行い、架橋、硬化したプライマ一層を設けた。Example 1 A radiation-curable paint was prepared by mixing and dissolving 40 parts of the resin composition (a), 41flS of carbon black (2 parts mp), and 0 parts of a solvent (luene/methyl ethyl ketone = 1/1). This paint was applied onto a polyester film to a dry film thickness of α5μ, and after drying,
Electron beam irradiation was performed in an atmosphere of N at an irradiation dose of 2 Mrad using an electrocurtain type electron beam irradiation device manufactured by SI, and a single layer of crosslinked and hardened primer was provided.

次いで下記の磁性塗料をこの上に乾燥厚２．５μｍとな
るように塗布し、乾燥後、表面平滑化処理を施し、１部
２インチ巾に裁断し、ビデオテープを得た。Next, the following magnetic paint was applied thereon to a dry thickness of 2.5 μm, and after drying, a surface smoothing treatment was performed, and portions were cut into 2-inch widths to obtain video tapes.

磁性塗料の製法 ニトロセルロース（旭化成（株）製Ｈ１／２’）　８部
ＶＡＧＨ（ユニオンカーバイド社ｇ）　１　０部ウレタ
ンエラストマー（グツドリッチ社、エステル５７０３）
メチルイソブチルケトン　１５０部 シクロヘキサノン　５０部 より得られた樹脂溶液に、 Ｆｅ−Ｎ１−Ｇｏ合金粉末　１００部 α−ＡＩ、０．（α５μ粒状）　２部 潤滑剤（高級脂肪酸変性シリコンオイル）　１部分散剤
（大豆油精製レシチン）　３部 ヲ配合し、ボールミルにて２４時間分散さセ、磁性塗料
を調製した。Manufacturing method of magnetic paint Nitrocellulose (H1/2' manufactured by Asahi Kasei Corporation) 8 parts VAGH (Union Carbide Co., Ltd.) 1 0 parts Urethane elastomer (Gutdrich Co., Ltd., Ester 5703)
To a resin solution obtained from 150 parts of methyl isobutyl ketone and 50 parts of cyclohexanone were added 100 parts of Fe-N1-Go alloy powder, α-AI, and 0.5 parts of Fe-N1-Go alloy powder. (α5μ granules) 2 parts lubricant (higher fatty acid modified silicone oil) 1 part powder (soybean oil refined lecithin) 3 parts were blended and dispersed in a ball mill for 24 hours to prepare a magnetic paint.

実施例２ カーボンブラック（６０ｍμ）　２０部前記樹脂組成物
（ａ）　４０部 前記樹脂組成物（ｂ）４部 溶ｍ（）ルエン／メチルエチルケトン＝１７１）　５６
９上記組成物の混合物を良く混合溶解させ、放射線硬化
性アンダーコート用塗料を調製した。この塗料を、ポリ
エステルフィルム上に乾燥を行った後にｇｓｌ：Ｗ、エ
レクトロカーテン型電子線加速装置を用いて、加速電圧
１６０ＫＶ電極電流１０ｍＡ　、照射線量３Ｍランドの
条件でＮ、雰囲気下で電子線を照射し、塗膜を硬化させ
プライマ一層を設けた。実施例１と同様に磁性層を形成
した。Example 2 Carbon black (60 mμ) 20 parts Said resin composition (a) 40 parts Said resin composition (b) 4 parts Dissolved m() Luene/Methyl ethyl ketone = 171) 56
9 The mixture of the above compositions was thoroughly mixed and dissolved to prepare a radiation-curable undercoating paint. After drying this paint on a polyester film, using an electrocurtain type electron beam accelerator using GSL:W, an electron beam was applied in an N atmosphere at an acceleration voltage of 160 KV and an electrode current of 10 mA, and an irradiation dose of 3 M land. The coating was irradiated to cure the coating and a single layer of primer was applied. A magnetic layer was formed in the same manner as in Example 1.

実施例３ カーボンブラック（８０ｍμ）　１０部前記樹脂組成物
（ｃ）７部 ＮＫエステル−Ａ−４Ｇ（新中村化学製）　３部溶剤（
）ルエン／メチルエチルケトン−１／１）　９０ｍ上記
組成物の混合物を良く混合溶解させ、放射線硬化性アン
ダーコート用塗料を調製した。この塗料をポリエステル
フィルム上に乾燥膜厚０．２μになるように塗布し、乾
燥を行った後に、照射線量５Ｍラッドの条件でＮ２雰囲
気下で、電子線照射を行い架橋硬化したプライマ一層を
設けた。次いで実施例１と同様の方法で磁性層を設はビ
デオテープを作製した。Example 3 Carbon black (80 mμ) 10 parts The resin composition (c) 7 parts NK ester-A-4G (manufactured by Shin Nakamura Chemical) 3 parts Solvent (
) Luene/Methyl Ethyl Ketone - 1/1) 90m The mixture of the above compositions was thoroughly mixed and dissolved to prepare a radiation-curable undercoating paint. This paint was applied to a polyester film to a dry film thickness of 0.2μ, and after drying, a single layer of cross-linked and cured primer was applied by electron beam irradiation in an N2 atmosphere at an irradiation dose of 5 Mrad. Ta. Next, a magnetic layer was provided in the same manner as in Example 1 to produce a videotape.

実施例４ カーボンブラック（３０ｍμ）　５部 前記樹脂組成物（ｂ）６部 前記樹脂組成物（ｅ）３部 １．６ヘキサングリコールジアクリレート　１部溶剤（
トルエン／メチルエチルケトン＝１／１　）　９０部上
記組成物の混合物を良く混合溶解させ放射線硬化性アン
ダーコート用塗料を調製した。この塗料をポリエステル
フィルム上に乾燥膜厚０．１μになるよ−うをこ塗布し
、乾燥を行なった後に、照射線量２Ｍランドの条件でＮ
、雰囲気下で電子線照射を行い、架橋硬化したプライイ
一層を設けた。次いで、この上に次の磁性層を形成した
。Example 4 5 parts of carbon black (30 mμ) 6 parts of the resin composition (b) 3 parts of the resin composition (e) 1.6 parts Hexane glycol diacrylate 1 part Solvent (
Toluene/methyl ethyl ketone = 1/1) 90 parts The mixture of the above compositions was thoroughly mixed and dissolved to prepare a radiation-curable undercoating paint. This paint was applied on a polyester film to a dry film thickness of 0.1μ, and after drying, N
A single layer of crosslinked and cured ply was provided by electron beam irradiation in an atmosphere. Next, the next magnetic layer was formed thereon.

（放射線硬化性磁性層） １００部 分散剤（オレイン酸）　２部 溶ｍ（メチルエチルケトン／トルエン＝５０７５０）１
００部 上記組成物を強力ミキサーにて３時間混合し、次に、 ビニライトＶＡＧＨ５部 溶剤（メチルエチルケトン／トルエン＝５０１５０　）
２００部 高級脂肪酸（ミリスチン酸）　３部 を用いて実施例１と同様に磁性塗料とし、この磁性塗料
を同様に塗布し、表面平滑処理後、加速電圧１５０Ｋｅ
Ｖ、電流１０ｆｆｌＡ、吸収線ｆｉｌ　５　Ｍ、ｒ　ｍ
　ｄの条件でＮ、雰囲気下にて電子線を照射し、塗膜を
硬化させた。(Radiation-curable magnetic layer) 100 parts dispersant (oleic acid) 2 parts solution m (methyl ethyl ketone/toluene = 50750) 1
00 parts The above composition was mixed for 3 hours with a powerful mixer, then 5 parts of Vinyrite VAGH solvent (methyl ethyl ketone/toluene = 50150)
A magnetic paint was prepared in the same manner as in Example 1 using 200 parts and 3 parts of higher fatty acid (myristic acid), and this magnetic paint was applied in the same manner as in Example 1. After surface smoothing treatment, an acceleration voltage of 150 Ke was applied.
V, current 10fflA, absorption line fil 5 M, r m
The coating film was cured by irradiation with an electron beam under N atmosphere under the conditions of d.

比較例１ 塩化ビニル・酢酸ビニル共ホ合体 （ユニオン・カーバイド＆＠ＶＡＧＨ）　１　０　ｆｆ
Ｍ％Ｆ剤（）ルエン／メチルエチルケトン＝１７１）　
９０部上記組成物を混合溶解した塗料をポリエステルフ
ィルムに乾燥厚０．１μになるように塗布し、乾燥し、
アンダーコート層を形成したほかは実施例１と同様の方
法で磁性層を設はビデオテープを作製した。Comparative Example 1 Vinyl chloride/vinyl acetate copolymer (Union Carbide & @VAGH) 1 0 ff
M% F agent () toluene/methyl ethyl ketone = 171)
A paint obtained by mixing and dissolving 90 parts of the above composition is applied to a polyester film to a dry thickness of 0.1μ, dried,
A videotape with a magnetic layer was prepared in the same manner as in Example 1 except that an undercoat layer was formed.

比較例２ 前記樹脂組成物（１）　ｓ　ｏ部 ｆｆｉ剤（）ルエン／メチルエチルケトン＝１／Ｎ）　
５０ｍ上記組成物を混合溶解し、放射線硬化性塗料を調
製し、実施例１と同様の方法でビデオテープを作製した
。Comparative Example 2 The resin composition (1) s o part ffi agent () luene/methyl ethyl ketone = 1/N)
A radiation-curable coating material was prepared by mixing and dissolving 50 m of the above composition, and a videotape was produced in the same manner as in Example 1.

実施例１〜４、比較例１〜２のサンプルについて、塗膜
の剥離強度およびＶＨＳデツキでのビデオ感度（ＲＦ４
ＭＨ２）を測定した結果を表１に示す。Regarding the samples of Examples 1 to 4 and Comparative Examples 1 to 2, the peel strength of the coating film and the video sensitivity (RF4
Table 1 shows the results of measuring MH2).

接着性についてはプライマ一層を形成したサンプルはい
ずれもカーボンブラックの入らない比較例１．２よりも
大きい接着強度を示した。Regarding adhesion, all the samples in which a single layer of primer was formed showed greater adhesive strength than Comparative Example 1.2, which did not contain carbon black.

光透過性については本発明のものはいずれも０５％以下
となり、極端に低くなり、比較例１．２のものに比して
はるかに小さい光透過率を有した。Regarding the light transmittance, all of the products of the present invention had an extremely low light transmittance of 0.05% or less, and had a much lower light transmittance than that of Comparative Example 1.2.

また磁性面の表面抵抗についてはｉｏ’〜１０”Ω／ｃ
ｍ’程度であり、ドロップアウトの数値からも本発明の
ものがすぐれていることが分る。In addition, the surface resistance of the magnetic surface is io'~10"Ω/c
m', and it can be seen from the dropout value that the method of the present invention is superior.

応 なおドロップアウトは４０℃、６０％ＲＨの条件での値
である。×は不良、◎は侵である。The corresponding dropout is the value under the conditions of 40° C. and 60% RH. × indicates defective, ◎ indicates violation.

以上のように、本発明では表面に露出した部分に導電処
理を施さないでプライマ一層にのみ導電性を賦与しただ
けで帯電の減少、巻姿の改善その他の効果゛が達成され
るから、バック層や表面層を形成する工程を全く必要と
しない。As described above, in the present invention, by imparting conductivity to only one layer of the primer without applying conductive treatment to the surface-exposed portion, reduction in charging, improvement in winding shape, and other effects can be achieved. There is no need for any process to form layers or surface layers.

代理人の氏名　倉　内　基　弘　□′ｊ第１頁の続き ０発　明　者　斉　藤　善　明　東京都中央区印式会社
内Agent's name Motohiro Kurauchi □'jContinued from page 1 0 Inventor Yoshiaki Saito Inside Inshikisha, Chuo-ku, Tokyo

Claims (2)

【特許請求の範囲】[Claims] （１）　透明プラスチックフィルム支持体と、その表面
に形成した下塗り層と、該下塗り層の表面に形成した磁
気記録用磁性層とから成る磁気記録媒体において、前記
下塗り層が、放射線により硬化する不飽和二重結合を１
分子当り１個以上含むオリゴマーまたはポリマーの１種
以上にカーボンブラックを分肢させて放射線硬化したも
のであることを特徴とする磁気記録媒体。(1) A magnetic recording medium comprising a transparent plastic film support, an undercoat layer formed on the surface thereof, and a magnetic recording layer formed on the surface of the undercoat layer, in which the undercoat layer is a non-hardening material that is cured by radiation. 1 saturated double bond
1. A magnetic recording medium comprising one or more oligomers or polymers containing at least one carbon black per molecule and radiation-cured. （２）　カーボンブラックはオリゴマーまたはポリマー
１００重量部当り５〜２００重景部用置部れている特許
請求の範囲第１項記載の磁気記録媒体。(2) The magnetic recording medium according to claim 1, wherein the carbon black is contained in an amount of 5 to 200 parts per 100 parts by weight of the oligomer or polymer.
JP58144413A 1983-08-09 1983-08-09 Magnetic recording medium Pending JPS6038723A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP58144413A JPS6038723A (en) 1983-08-09 1983-08-09 Magnetic recording medium
US06/631,208 US4596747A (en) 1983-08-09 1984-07-16 Magnetic recording medium
DE3428943A DE3428943C2 (en) 1983-08-09 1984-08-06 Magnetic recording medium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58144413A JPS6038723A (en) 1983-08-09 1983-08-09 Magnetic recording medium

Publications (1)

Publication Number Publication Date
JPS6038723A true JPS6038723A (en) 1985-02-28

Family

ID=15361591

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58144413A Pending JPS6038723A (en) 1983-08-09 1983-08-09 Magnetic recording medium

Country Status (3)

Country Link
US (1) US4596747A (en)
JP (1) JPS6038723A (en)
DE (1) DE3428943C2 (en)

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JPS60251510A (en) * 1984-05-28 1985-12-12 Fuji Photo Film Co Ltd Magnetic recording medium
JPS63161517A (en) * 1986-12-25 1988-07-05 Toyobo Co Ltd Magnetic recording medium
US6127039A (en) * 1998-01-23 2000-10-03 Tdk Corporation Magnetic recording medium and a process for producing the same
US20130333978A1 (en) * 2011-03-03 2013-12-19 Nitto Denko Corporation Waterproof sound-transmitting membrane and electrical product

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US4933221A (en) * 1984-07-31 1990-06-12 Canon Kabushiki Kaisha Optical recording device
DE3609261C2 (en) * 1985-03-19 1997-03-06 Tdk Corp Magnetic recording medium
JP2500934B2 (en) * 1985-03-27 1996-05-29 ティーディーケイ株式会社 Magnetic recording media
JPH0760511B2 (en) * 1985-06-26 1995-06-28 株式会社東芝 High durability magnetic recording medium
JPS62227745A (en) * 1986-03-31 1987-10-06 ダイアホイルヘキスト株式会社 Magnetic record medium
US4801392A (en) * 1987-07-02 1989-01-31 The Mead Corporation Magnetic recording compositions containing ionic dye compounds as initiators
JP2566091B2 (en) * 1992-01-31 1996-12-25 富士写真フイルム株式会社 Magnetic recording media
US6331342B1 (en) * 1996-07-08 2001-12-18 Sony Corporation Magnetic recording medium
DE19851567A1 (en) * 1998-11-09 2000-05-11 Emtec Magnetics Gmbh Binder composition for magnetic recording media and photoinitiator mixture curable by UV radiation
JP2002352410A (en) * 2001-05-22 2002-12-06 Fuji Photo Film Co Ltd Magnetic recording medium
JP2004185713A (en) * 2002-12-03 2004-07-02 Fuji Photo Film Co Ltd Magnetic recording medium
JP4045498B2 (en) * 2003-03-25 2008-02-13 富士フイルム株式会社 Magnetic recording medium
JP2006351125A (en) * 2005-06-17 2006-12-28 Tdk Corp Magnetic recording medium

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60251510A (en) * 1984-05-28 1985-12-12 Fuji Photo Film Co Ltd Magnetic recording medium
JPH0522968B2 (en) * 1984-05-28 1993-03-31 Fuji Photo Film Co Ltd
JPS63161517A (en) * 1986-12-25 1988-07-05 Toyobo Co Ltd Magnetic recording medium
US6127039A (en) * 1998-01-23 2000-10-03 Tdk Corporation Magnetic recording medium and a process for producing the same
US20130333978A1 (en) * 2011-03-03 2013-12-19 Nitto Denko Corporation Waterproof sound-transmitting membrane and electrical product
US9171535B2 (en) * 2011-03-03 2015-10-27 Nitto Denko Corporation Waterproof sound-transmitting membrane and electrical product

Also Published As

Publication number Publication date
US4596747A (en) 1986-06-24
DE3428943C2 (en) 1995-11-23
DE3428943A1 (en) 1985-02-28

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